含氟聚酰亚胺及其在微电子工业中的研究进展Ⅰ含氟单体及聚酰亚胺的合成

综述了近年来国内外在含氟聚酰亚胺(PI)研究及应用领域中的最新进展情况.主要从含氟二胺单体、二酐单体及含氟聚酰亚胺在合成方面的研究进展情况进行了详细的综述.重点阐述了中国科学院化学研究所305组近几年在这方面的研究进展情况,并指出为了推动含氟聚酰亚胺这类具有优良综合性能的功能材料在工业上的广泛应用,就必须首先解决含氟单体种类较少这个制约含氟聚酰亚胺发展的瓶颈问题.     

含氟聚酰亚胺的研究进展

综述了含氟聚酰亚胺研究的新进展,介绍了含氟单体,聚合物合成方法及主要性质。着重介绍了含氟聚酰亚胺的物理化学性质,光学和电学性能以及气体选择透过性。同时简述全氟代聚酰亚胺的合成,性能及应用前景。     

含氟聚酰亚胺及其在微电子工业中的研究进展Ⅱ含氟聚酰亚胺在微电子工业中的应用

综述了近年来国内外在含氟聚酰亚胺(PI)研究及应用领域中的最新进展情况。主要从现代微电子工业对相关材料的性能要求、标准型聚酰亚胺材料所面临的挑战以及新型含氟聚酰亚胺在微电子工业中的应用等几个方面进行了详细的综述。重点阐述了中国科学院化学研究所305组近几年在这方面的研究进展情况。并指出为了推动我国微电子工业的发展，研制开发低成本、高技术含量的含氟聚酰亚胺材料具有十分重要的现实意义．     

一种高可溶、高光学透明含氟聚酰亚胺的合成与表征

由自制芳香二胺单体9,9-双(3,5-二氟-4-胺基苯基)芴和商品化二酐单体4,4'-(六氟异丙基)双邻苯二甲酸酐经一步法高温缩聚制备了一种新型含氟聚酰亚胺.分别用FT-IR、1HNMR和19FNMR对所制聚酰亚胺结构进行了表征.结果证实其与所设计的结构完全一致,并且酰亚胺化反应完全.该含氟聚酰亚胺表现出高的溶解性:室温下在N-甲基-2-吡咯烷酮、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、氯仿、二氯甲烷、四氢呋喃等常规溶剂中的溶解度可达10wt%以上.由该聚酰亚胺溶液所制的薄膜无色透明,截断波长在315nm,400nm波长后的透光率在84%以上.此外该含氟聚酰亚胺还表现出良好的热学性能和机械性能:玻璃化转变温度在377℃,空气和氮气中10%热失重温度均在539℃以上;其薄膜的拉伸强度在70～80MPa,断裂伸长率在4%～8%,起始模量为2.6GPa.     

含氟芳杂环高分子及其在微电子工业中的研究进展

综述了近年来国内外在含氟芳杂环高分子方面的研究及应用进展情况。主要介绍了含氟聚苯并睬咪唑(PBI)、聚苯并喏唑(PBO)、聚芳醚(PAE)及其衍生物等材料。从含氟单体的合成、聚合物的合成及其应用等几个方面进行了阐述。     

含氟硅聚合物的合成及应用

含氟硅聚合物作为一种新型材料,有机结合了含氟聚合物和含硅聚合物的优点,成为材料领域研究开发的热点之一。本文综述了含氟硅聚合物合成的研究进展,介绍了其应用情况。     

含氟聚酰亚胺接枝低聚倍半硅氧烷制备超低介电材料

含氟聚酰亚胺接枝低聚倍半硅氧烷制备超低介电材料;介电常数;纳米复合材料;低聚倍半硅氧烷;接枝共聚;含氟聚酰亚胺     

含氟苯硼酸的合成及应用研究进展

含氟苯硼酸是一种重要的有机合成中间体, 在有机合成中应用相当广泛. 综述了近年来含氟苯硼酸的合成及应用方面的重要研究进展.     

主链含氟聚酰亚胺液晶取向排列剂的表面性能及微观形貌

主链含氟聚酰亚胺液晶取向排列剂的表面性能及微观形貌     

脂环族聚酰亚胺及其液晶取向膜材料

综述了近年来在脂环族聚酰亚胺领域内的研究进展,从单体的合成方法和分类以及脂环族聚酰亚胺的合成方法和实际应用等几方面系统阐述了该领域的研究进展,并着重讨论了其作为液晶显示器取向膜材料中的应用。     

ATRP法合成含氟丙烯酸酯类聚合物的研究进展

含氟丙烯酸酯聚合物由于氟原子的改性作用而具有优异的表面特性,不仅稳定,具有很好的耐氧化和耐腐蚀性,而且具有较好的耐水、耐油及耐污性,可望在新材料的开发、理论研究和实际应用等方面获得广泛的应用.而原子转移自由基聚合(ATRP)又可为分子设计和合成提供很有效的途径,利用这种聚合可以获得预期结构和性能的含氟嵌段聚合物材料,充分发挥含氟元素的改性作用.本文综述了ATRP在丙烯酸氟烷基酯聚合物合成方面的应用,并介绍了国内外在此领域的研究状况.     

Sul-containing fluorinated polyimides for optical waveguide device

Novel sul-containing fluorinated polyimides have been synthesized by the reaction of 2,2′-bis-(trifluoromethyl)-4,4′-diaminodiphenyl sulfide (TFDAS) with 1,4-bis-(3,4-dicarboxyphenoxy)benzene dianhydride (HQDPA), 2,2′-bis-(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA), 4,4′-oxydiphthalicanhydride (ODPA) or 3,4,3′,4′-biphenyl-tetracarboxylic acid dianhydride (s-BPDA). The fluorinated polyimides, prepared by a one-step polycondensation procedure, have good solubility in many solvents, such as N-methyl-2-pyrrolidinone (NMP), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), cyclohexanone, tetrahydrofuran (THF) and m-cresol. The molecular weights (M_n's) and polydispersities (M_n/M_w's) of polyimides were in the range of 1.24 × 10⁵ to 3.21 × 10⁵ and 1.59–2.20, respectively. The polymers exhibit excellent thermal stabilities, with glass-transition temperatures (T_g) at 221–275 °C and the 5% weight-loss temperature are above 531 °C. After crosslinking, these polymers show higher thermal stability. The films of polymers have high optical transparency. The novel sul-containing fluorinated polyimides also have low absorption at both 1310 and 1550 nm wavelength windows. Rib-type optical waveguide device was fabricated using the fluorinated polyimides and the near-field mode pattern of the waveguide was demonstrated.     

核壳型含氟丙烯酸酯共聚物的合成及性能

采用饥饿态半连续种子乳液聚合方法, 在十二烷基硫酸钠(SDS)/辛基苯基聚氧乙烯醚(TX-10)复合乳化剂的作用下, 分别选用甲基丙烯酸三氟乙酯(TFEM)、甲基丙烯酸六氟正丁酯(HFBM)和甲基丙烯酸十二氟庚酯(DFHM)为含氟单体, 合成以丙烯酸正丁酯(BA)、甲基丙烯酸甲酯(MMA)和含氟单体为原料的核壳型结构含氟丙烯酸酯共聚物乳液. FTIR, 1H NMR, TEM和DSC分析结果显示, 获得了BA/MMA/含氟单体的共聚物乳液, 且乳液具有明显的核壳结构. DSC, TGA和SEM-EDX的分析显示, 核壳型结构的共聚物具有优异的热力学稳定性能和成膜性能; 长侧链或短侧链含氟单体对共聚物的热稳定性影响不明显, 但侧链较长的含氟单体所获得的聚合物在成膜过程中更易向表面迁移, 更能体现含氟聚合物的优点.     

活性聚合法合成结构精确的含氟嵌段共聚物

结构精确的含氟嵌段共聚物具有优异而独特的化学和物理性能,有广阔的应用前景,因此受到广泛的关注.含氟嵌段共聚物可分为两类,一类是侧基含氟嵌段共聚物,另一类是主链含氟嵌段共聚物.活性聚合为嵌段共聚物的合成提供了最为重要的方法,利用它可以合成结构精确、分子量可控、分子量分布窄的嵌段共聚物.根据单体的反应特性选择不同的聚合方法,可以得到不同的含氟嵌段共聚物.本文主要综述了近几年利用各种活性聚合方法合成结构精确的含氟嵌段共聚物方面的进展.     

Update on fluoroelastomers: from perfluoroelastomers to fluorosilicones and fluorophosphazenes

A survey of the synthesis, properties and applications of fluoroelastomers is reported falling into two main parts. After describing commercially available (per)fluorocarbon elastomers, fluoro-phosphazenes and silicones, recent data on hybrid fluorosilicones containing longer chains (often fluorinated) between silicon atoms are supplied. The second part deals with well-architectured fluoroelastomers. First, fluorinated thermoplastic elastomers obtained either by sequential iodine transfer polymerisation of fluoroalkenes (leading to triblock copolymers) or by a two-step procedure involving a monomer bearing peroxide that generated macroperoxides which thus produced graft copolymers. Then, multiblock copolymers were achieved either from telechelic perfluoropolyethers or from polyhydrosilylation of telechelic non-conjugated diene polyimides with fluorinated polyhybrid siloxane bearing Si-H end groups leading to exceptional materials.     

Synthesis of New Fluoropolymers: Tailoring Macromolecular Properties with Fluorinated Substituents

The challenges and opportunities in the preparation of new fluoro- polymers are illustrated by the synthesis of fluorinated poly(ether sulfones), polyimides, and polyethers. Synthetic methods used for the preparation of new fluorinated monomers and polymers include anion-radical substitutions of perfluoroalkyl diiodides, nucleophilic additions to fluorinated olefins, perfluoroalkylsulfonyl-mediated nucleophilic sub-stitutions, and direct fluorinations with elemental fluorine. Properly placed fluorinated substituents can have significant effects on the dielectric properties, thermal stability, moisture absorption, permeability, phase transitions, and reactivity of the resulting polymers. In addition, fluorinated groups can enhance nonlinear optical effects and provide a method for chromophore alignment. The special behavior of partially fluorinated substituent groups offers unique tools for tailoring macro-molecular properties.     

Synthesis and characterization of novel fluorinated polyimides derived from 1,1′-bis(4-aminophenyl)-1-(3-trifluoromethylphenyl)-2,2,2-trifluoroethane and aromatic dianhydrides

A novel fluorinated aromatic diamine 1,1′-bis(4-aminophenyl)-1-(3-trifluoromethylphenyl)-2,2,2-trifluoroethane (6FDAM) was synthesized in a simple procedure, which was then employed to prepare a series of fluorinated polyimides with commercial aromatic dianhydrides, such as pyromellitic dianhydride (PMDA), 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane (6FDA), 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA) and 4,4′-oxydiphthalic anhydride (ODPA). The polyimides exhibited good solubility in strong dipolar solvents such as NMP, DMAc, DMF and m-cresol as well as some of low boiling point organic solvents of THF and CHCl₃, etc. Experimental results indicated the polyimides possessed low moisture adsorptions of 0.42-0.95%, low dielectric constant of 2.71-2.95 at 1 MHz, high dielectric strength of 92.0-122.6 kV/mm and good optical transparency with cutoff wavelengths of UV-vis at 330-375 nm. The polyimides also exhibited good mechanical properties as well as excellent thermal and thermo-oxidative stability. The fluorinated polyimides possessed better solubility, lower dielectric constant and water adsorption as well as higher optical transparency than the representative non-fluorinated polyimide derived from PMDA and 4,4′-oxydianiline (ODA).     

ORGANO-SOLUBLE FLUORINATED POLYIMIDES DERIVED FROM α,α-BIS(4-AMINO-3,5- DIMETHYLPHENYL)-4''-FLUOROPHENYL METHANE AND VARIOUS AROMATIC DIANHYDRIDES

Organo-soluble fluorinated polyimides were synthesized by the polycondensation of a new aromatic diamine α,αbis(4-amino-3,5-dimethylphenyl)-4'-fluorophenyl methane with several aromatic dianhydrides. The one-step polymerization polyimides could be soluble not only in polar aprotic solvents, such as N-methyl-2-pyrrolidinone, and N,Ndimethylacetamide, but also in common organic solvents, such as chloroform, cyclopentanone, m-cresol and so on. The polyimide films show excellent transparency with the UV-Vis cut-off lengths of 310-360 nm and light transmittances of higher than 80% in the visible region. In addition, the polyimides exhibit good thermal stability with an initial decomposition temperature (Td) higher than 530℃ and have more than 60% of residual weight retentions at 700 ℃.     

Synthesis and characterization of novel fluorinated polyimides derived from 4-phenyl-2,6-bis[4-(4′-amino-2′-trifluoromethyl-phenoxy)phenyl]pyridine and dianhydrides

A series of organo-soluble polyimides were prepared from a novel fluorinated diamine monomer, 4-phenyl-2,6-bis[4-(4′-amino-2′-trifluoromethylphenoxy)phenyl]pyridine and various commercial aromatic dianhydrides. These polyimides had good solubility in common organic solvents. The obtained strong and flexible PI films exhibited excellent thermal stability with the decomposition temperature (at 5% weight loss) of above 561 °C and the glass transition temperature in the range of 258-312 °C. Moreover, the polymer films showed good electrical insulating property, low dielectric constant and low water uptake due to the introduction of fluorinated substitutes in the polymer backbone. The remarkable combined features ensure these polymers to be ideal candidate materials for advanced microelectronic industry and other related applications.